现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (11) : 133-137. DOI: 10.16606/j.cnki.issn0253-4320.2025.11.024

科研与开发

S型异质结BiOBr/In₂O₃光催化CO₂还原为乙醇的性能研究

作者信息 +

Study on performance of S-type heterojunction BiOBr/In₂O₃ in photocatalytic reduction of CO₂ to ethanol

Author information +

文章历史 +

Received		Published
2025-02-27		2025-11-20
Issue Date	Revised Date
2025-11-17	2025-02-27

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摘要

采用高温煅烧和水热合成的方法制备了BiOBr、In₂O₃及BiOBr/In₂O₃异质结,用于光催化CO₂还原制备乙醇。结果表明,在只有水和CO₂的条件下,光照5 h,单独的In₂O₃并无乙醇生成,其绝大部分产物为CO;单独的BiOBr有极少量的乙醇生成,而BiOBr/In₂O₃异质结乙醇的产率达到了43.2 μmol/(g·h),且选择性达到了55.99%。通过XRD、SEM、TEM、XPS、UV-Vis DRS、EIS等对BiOBr、In₂O₃及BiOBr/In₂O₃异质结的结构和机理进行了分析。结果表明,BiOBr与In₂O₃之间独特的异质结构,促进了光生电子的传输,极大地提高了乙醇产率和选择性。

Abstract

BiOBr,In₂O₃ and BiOBr/In₂O₃ heterojunction are prepared via high-temperature calcination and hydrothermal synthesis methods,and applied for the photocatalytic reduction of CO₂ to ethanol.Experimental results show that under the conditions of water,CO₂ and 5 h of light exposure,there is no ethanol generated over In₂O₃ alone,and CO is the majority product;there is a very small amount of ethanol generated over BiOBr alone,while the yield of ethanol over BiOBr/In₂O₃ heterojunction reaches 43.2 μmol/(g·h) with a selectivity of 55.99%.The structure and catalytic mechanism of BiOBr,In₂O₃ and BiOBr/In₂O₃ heterojunction are characterized by means of XRD,SEM,TEM,XPS,UV-Vis DRS,and EIS.It is shown that the unique heterostructure between BiOBr and In₂O₃ promotes the transport of photogenerated electrons,which greatly improves the yield and selectivity of ethanol.

Graphical abstract

关键词

BiOBr/In₂O₃ / 异质结 / 乙醇 / CO₂还原 / 光催化

Key words

BiOBr/In₂O₃ / heterojunction / ethanol / CO₂ reduction / photocatalytic

Author summay

蔡嘉俊(1999-),男,硕士生,研究方向为光催化CO₂还原,1728761940@qq.com

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S型异质结BiOBr/In₂O₃光催化CO₂还原为乙醇的性能研究[J]. 现代化工, 2025, 45(11): 133-137 DOI:10.16606/j.cnki.issn0253-4320.2025.11.024

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近些年由于CO₂的过度排放,导致全球气候变暖,将CO₂转化为高附加值的燃料可以有效缓解化石资源枯竭和环境变暖问题^[1-3]。通过光催化将CO₂和H₂O还原为高附加的燃料被认为是解决化石资源枯竭和环境变暖问题的一种重要手段^[4-5]。常见的光催化CO₂还原产物有CO、CH₄、甲醇、乙醇等,其中绝大多数的C₁产物存在着能量密度较低、存储运输不方便的问题,而乙醇作为一种C₂产物,其能量密度很高,且便于运输和存储,有广阔的应用前景^[6-9]。而利用可见光将CO₂和H₂O催化为乙醇有一个很大的难点,即乙醇需要参与反应的电子数目多达12个,这就需要电子的传输速率足够高^[10]。这个问题制约了乙醇的进一步生成和应用^[11]。

最近的研究表明,Bi³⁺金属半导体具有降低C—C耦合能垒的能力,被认为是用来制备乙醇的一类催化剂^[12]。近些年来,一些Bi³⁺金属半导体催化剂,如Bi₁₉S₂₇

${C{l}_{3}}$

^[13]、Bi₂

${{MoO}_{6}}$

^[14]、BiOCl^[15]、Bi₂

${{S}_{3}}$

^[16]等已经被用于光催化CO₂和H₂O制备乙醇。而BiOBr作为其中的一种Bi³⁺材料,其较窄的带隙对于可见光有着良好的响应,被认为是适合用来制备乙醇的催化剂,但由于其电子复合率高,限制了其进一步生成乙醇^[17]。而构造异质结构被认为是解决电子复合率高的一种有效手段,In₂O₃作为一种带隙较宽的半导体,其化学性质非常稳定,且电子复合率相较而言比较低,若与BiOBr形成异质结可以有效减少电子与空穴的复合,从而进一步提高乙醇的产率,且在光催化CO₂过程中,In₂O₃还易于生成CO,有利于提高C—C耦合中间体 ^*CO的覆盖率^[18]。

本文通过煅烧和水热法合成BiOBr/In₂O₃复合催化剂,用于光催化CO₂和H₂O还原制备乙醇。

1 材料与试剂

1.1 材料和试剂

Bi(NO₃)₃·5H₂O(99%)、溴化钾(KBr,99%)购买自上海阿拉丁生化科技股份有限公司;In(NO₃)₃·xH₂O(99%)购买自上海泰坦科技股份有限公司;Y(NO₃)₃·6H₂O(99%)购买自上海麦克林生化科技股份有限公司;尿素(99%)购买自西陇科学股份有限公司。所有化学药品不经提纯直接使用。实验过程中使用的去离子水均为实验室自制。

1.2 催化剂的制备

In₂O₃的制备:先将1.5 g的In(NO₃)₃·xH₂O加入到盛有80 mL去离子水的烧杯中,搅拌1 h,然后将搅拌后的溶液转移至100 mL不锈钢高压釜内衬于125℃加热反应4 h;反应后的沉积物用去离子水洗涤数次,最后将洗涤后的样品放入60℃真空干燥箱中进行干燥;将干燥得到的In(OH)₃放入到氧化铝坩埚当中,以5℃/min升温至350℃,煅烧4 h,得到In₂O₃。

BiOBr/In₂O₃异质结的制备:先将1 mmol的 Bi(NO₃)₃·5H₂O和1 mmol的KBr加入到盛有 60 mL去离子水的烧杯中,搅拌1 h,然后加入 1 mmol的In₂O₃,再搅拌1 h,将搅拌后的溶液转移至100 mL不锈钢高压釜内衬于160℃加热反应 24 h;反应后的沉积物用去离子水洗涤数次,最后将洗涤后的样品放入60℃真空干燥箱中进行干燥,得到BiOBr/In₂O₃异质结。

1.3 材料表征

采用Cu K_α辐射源(λ=0.154 06 nm)的X射线衍射(XRD,Anton Paar XRDynamic500,奥地利)对催化剂的相组成进行表征;通过扫描电子显微镜(SEM,ZEISS Sigma 300,德国)、具有能量散射系统(EDS)的透射电子显微镜(TEM,JEOL JEM-F200)对催化剂的形貌、组成和元素分布进行表征;采用X射线光电子能谱仪(XPS,Thermo Scientific K-Alpha,美国)分析催化剂的元素价态;通过原位XPS测试仪器(美国Thermofisher ESCALAB 250Xi)在300 W氙灯的照射下,进行原位XPS测试,分析在光照条件下,各个元素结合能的变化;通过紫外电子能谱(美国Thermo Fisher Scientific ESCALAB XI+)分析In₂O₃和BiOBr的费米能级。

1.4 光催化CO₂还原实验

先将10 mg催化剂加入到含有8 mL去离子水的离心管中,超声10 min,使其分散均匀;然后倒入到高压反应器中,持续通入30 min的N₂,并保持压力在0.1 MPa,排尽反应器内的空气,接着持续通入 30 min的CO₂,保持压力也在0.1 MPa,置换N₂,使反应器内充满CO₂。然后在300 W氙灯(中教金源CEL-HUVUV300)420 nm滤光片的照射和无牺牲剂的条件下,持续通入CO₂,连续反应5 h,将收集到的气液相产物,通入到配备热导检测器(TCD)和火焰离子化检测器(FID)的气相色谱仪(GC9790Ⅱ)中进行分析^[19]。

产物的产率[Y,μmol/(g·h)]计算公式:

(1)Y=n/(m·t)

其中:n为生成乙醇、CH₄、甲醇及CO的物质的量,mol;m为催化剂的质量,g;t为反应时间,h。

产物乙醇的选择性(S,%)计算公式^[20]:

(2)$\begin{array}{c} S=12 n(\text { 乙醇 }) /\left[12 n(\text { 乙醇 })+8 n\left(\mathrm{CH}_{4}\right)+6 n(\text { 甲醇 })+\right. \\ 2 n(\mathrm{CO})] \times 100 \% \end{array}$

1.5 光电化学测试

采用标准的三电极体系连接电化学工作站(CHI-660E)对催化剂进行阻抗、Mott-Schottky(MS)曲线和瞬态光电流的测试。对电极为铂电极,参比电极为Ag/AgCl。首先,将10 mg样品放入装有200 μL Nafion溶液(质量分数5.0%)和1 mL异丙醇的离心管中,超声1 h,得到均匀的悬浮液。然后在导电玻璃(1 cm×2 cm)上喷涂悬浮液制成工作电极,自然干燥。最后以0.5 mol/L Na₂SO₄溶液为电解液,在300 W氙灯下检测阻抗、Mott-Schottky(MS)和瞬态光电流^[21]。

2 结果与讨论

2.1 XRD分析

利用XRD对合成后的BiOBr、In₂O₃、BiOBr/In₂O₃异质结催化剂进行了物相表征,结果如图1所示。合成的BiOBr和In₂O₃的XRD物相基本上都能与标准卡片BiOBr PDF#78-0348及In₂O₃ PDF#88-2160对应。在BiOBr和In₂O₃复合形成BiOBr/In₂O₃异质结后,其XRD物相以BiOBr为主要成分,其中10.907°、31.718°、39.326°处的峰显示为 BiOBr的物相,30.585°、35.462°、51.024°处的峰显示为In₂O₃的物相。XRD谱图表明BiOBr和In₂O₃成功复合。

2.2 材料形貌分析

BiOBr/In₂O₃异质结的SEM和HRTEM形貌图如图2所示。BiOBr以层状的结构形式存在,而In₂O₃以小颗粒状不均匀地分散在层状BiOBr。BiOBr主要以(004)晶面为主,In₂O₃主要以(222)晶面为主,其中BiOBr的晶面间距为0.198 nm,而In₂O₃的晶面间距为0.295 nm。从BiOBr/In₂O₃的TEM物相中还发现,BiOBr、In₂O₃两者的晶格存在很明显的晶格分界,这说明BiOBr和In₂O₃之间确实存在着异质结构。

2.3 XPS分析

BiOBr、In₂O₃以及BiOBr/In₂O₃异质结的XPS谱图如图3所示。在形成复合材料BiOBr/In₂O₃异质结之后,BiOBr/In₂O₃异质结Bi 4f峰和Br 3d峰相较于单独的BiOBr都向低结合能的方向偏移,说明Bi元素和Br元素在整个过程中都处于得电子的状态。BiOBr/In₂O₃异质结In 3d峰相较于单独的In₂O₃向高结合能的方向偏移,说明In元素在整个过程中都处于失电子的状态。单独的BiOBr以Bi—O—Br的形式存在;而单独的In₂O₃以In—O的方式存在。在形成异质结之后BiOBr/In₂O₃中O 1s峰介于BiOBr和In₂O₃之间。这说明BiOBr/In₂O₃异质结之间存在着相互作用。

2.4 性能测试

图4是BiOBr、In₂O₃及BiOBr/In₂O₃异质结在只有水、CO₂以及光照的条件下,反应5 h测试得到的产率和选择性。单独的In₂O₃只有CO和CH₄生成,且绝大部分的产物为CO,这为后续C—C偶联提供了充足的 ^*CO。单独的BiOBr仅有少量乙醇生成,产率和选择性极低。将BiOBr与In₂O₃复合形成BiOBr/In₂O₃异质结之后,乙醇的产率和选择性得到了极大地提升,这归功于BiOBr与In₂O₃之间的相互作用。

2.5 紫外-可见漫反射光谱分析

图5(a)是BiOBr、In₂O₃及BiOBr/In₂O₃异质结的固体紫外-可见吸收光谱,根据半导体类型的不同,绘制了如图5(b)所示的带隙图。In₂O₃是直接半导体,根据固体紫外结果,求得其带隙为3.37 eV;而BiOBr及BiOBr/In₂O₃异质结为间接半导体,根据固体紫外-可见吸收光谱,求其带隙分别为2.58、2.74 eV。

In₂O₃的带隙非常大,说明其对于可见光的吸收较差,但同时其光生电子复合率较低;而BiOBr的带隙较窄,说明其对于可见光的吸收较强,但同时其光生电子复合率较高,不利于进一步的反应。BiOBr/In₂O₃异质结结合了BiOBr和In₂O₃的优点,对于可见光有着较好的吸收,同时也能在一定程度上减少光生电子的复合率。

2.6 光电化学测试分析

从图6(a)可以看出,BiOBr/In₂O₃异质结的阻抗最小,In₂O₃和BiOBr的阻抗都比较大。从图6(b)可以看出,BiOBr/In₂O₃异质结的光电流最大,达到约0.9 A/cm²,而In₂O₃和BiOBr的光电流都非常的小,不到0.1 A/cm²。这样的结果可以归因于BiOBr/In₂O₃异质结独特的结构,促进了电子传输和转移,从而使得更多的光生电子参与到反应当中。

2.7 机理分析

根据图7(a)和图7(c)测试结果得到BiOBr的导带为-0.83 eV,In₂O₃的导带为-0.38 eV。如图7(b)和图7(d)所示,BiOBr的功函数为17.05 eV,计算得到其费米能级为4.17 eV;In₂O₃的功函数为16.88 eV,计算得到其费米能级为4.34 eV。根据费米能级以及能带分布情况,绘制了图7(e)的BiOBr/In₂O₃异质结机理示意图。BiOBr/In₂O₃之间确实形成了S型异质结。

3 结论

本研究构建了一种异质结复合催化剂BiOBr/In₂O₃。BiOBr/In₂O₃催化剂具有优异的CO₂还原性能,其乙醇产率达到了43.2 μmol/(g·h),且选择性达到了55.99%。一系列表征证明,BiOBr与In₂O₃之间确实形成异质结。异质结的形成有效地促进了电子的传输,提高了光催化活性。这项研究为设计光催化CO₂和H₂O制备乙醇的复合材料提供了思路。

参考文献

原文顺序 | 出版日期 | 本文引用

[1]	江雨婷, 徐红, 钟毅, 等. MCM-41/NH₂-MIL-101(Fe)复合材料的制备及其光催化还原CO₂性能[J].现代化工, 2024, 44(S2):155-160.

[2]	曹泽宇, 张心爱, 张博, 等. 镍纳米颗粒调控MOF基镍-氮碳催化剂高效电催化还原CO₂的研究[J]. 现代化工, 2024, 44(1):94-100.

[3]	蔡静宇, 张春妮, 肖龙强, 等. MOF衍生Co-C/FeO_x复合材料的制备及其催化CO₂还原性能探究[J]. 现代化工, 2024, 44(1):153-158.

[4]	Peter S C. Reduction of CO₂ to chemicals and fuels:A Solution to global warming and energy crisis[J]. ACS Energy Letters, 2018, 3(7):1557-1561.

[5]	Fu J, Jiang K, Qiu X, et al. Product selectivity of photocatalytic CO₂ reduction reactions[J]. Materials Today, 2020, 32:222-243.

[6]	Zhang T, Li W, Huang K, et al. Regulation of functional groups on graphene quantum dots directs selective CO₂ to CH₄ conversion[J]. Nat Commun, 2021, 12(1):5265.

[7]	Wang G, He C T, Huang R, et al. Photoinduction of Cu single atoms decorated on UiO-66-NH₂ for enhanced photocatalytic reduction of CO₂ to liquid fuels[J]. J Am Chem Soc, 2020, 142(45):19339-19345.

[8]	Das R, Das K, Ray B, et al. Green transformation of CO₂ to ethanol using water and sunlight by the combined effect of naturally abundant red phosphorus and Bi₂MoO₆[J]. Energy & Environmental Science, 2022, 15(5):1967-1976.

[9]	Yu H, Sun C, Xuan Y, et al. Full solar spectrum driven plasmonic-assisted efficient photocatalytic CO₂ reduction to ethanol[J]. Chemical Engineering Journal, 2022, 430:13420.

[10]	Goud D, Gupta R, Maligal-Ganesh R, et al. Review of catalyst design and mechanistic studies for the production of olefins from anthropogenic CO₂[J]. ACS Catalysis, 2020, 10(23):14258-14282.

[11]	Nikoloudakis E, Lopez-Duarte I, Charalambidis G, et al. Porphyrins and phthalocyanines as biomimetic tools for photocatalytic H₂ production and CO₂ reduction[J]. Chem Soc Rev, 2022, 51(16):6965-7045.

[12]	Wang J, Heil T, Zhu B, et al. A single Cu-center containing enzyme-mimic enabling full photosynthesis under CO₂ reduction[J]. ACS Nano, 2020, 14(7):8584-8593.

[13]	Das K, Das R, Riyaz M, et al. Intrinsic charge polarization in Bi₁₉S₂₇Cl₃ nanorods promotes selective C—C coupling reaction during photoreduction of CO₂ to ethanol[J]. Adv Mater, 2023, 35(5):e2205994.

[14]	Dai W, Xiong W, Yu J, et al. Bi₂MoO₆ quantum dots in situ grown on reduced graphene oxide layers:A novel electron-rich interface for efficient CO₂ reduction[J]. ACS Appl Mater Interfaces, 2020, 12(23):25861-25874.

[15]	Sánchez-Rodríguez D, Jasso-Salcedo A B, Hedin N, et al. Semiconducting nanocrystalline bismuth oxychloride BiOCl for photocatalytic reduction of CO₂[J]. Catalysts, 2020, 10(9):998-1012.

[16]	Dai W, Yu J, Luo S, et al. WS₂ quantum dots seeding in Bi₂S₃ nanotubes:A novel Vis-NIR light sensitive photocatalyst with low-resistance junction interface for CO₂ reduction[J]. Chemical Engineering Journal, 2020, 389:123430.

[17]	Wang P, Yang P, Bai Y, et al. Synthesis of 3D BiOBr microspheres for enhanced photocatalytic CO₂ reduction[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 68:295-300.

[18]	Gong S, Ni B, He X, et al. Electronic modulation of a single-atom-based tandem catalyst boosts CO₂ photoreduction to ethanol[J]. Energy & Environmental Science, 2023, 16(12):5956-5969.

[19]	Zhang M, Mao Y, Bao X, et al. Coupling benzylamine oxidation with CO₂ photoconversion to ethanol over a black phosphorus and bismuth tungstate S-scheme heterojunction[J]. Angew Chem Int Ed Engl, 2023, 62(36):e202302919.

[20]	Li P, Qi Z, Yan D. Rare earth Er-Nd dual single-atomic catalysts for efficient visible-light induced CO₂ reduction to C_nH₂_n₊₁OH(n=1,2)[J]. Angew Chem Int Ed Engl, 2024, 63(49):e202411000.

[21]	Shi H, Wang H, Zhou Y, et al. Atomically dispersed indium-copper dual-metal active sites promoting C—C coupling for CO₂ photoreduction to ethanol[J]. Angew Chem Int Ed Engl, 2022, 61(40):e202208904.